Composition of matter and method of making same



Patented Mar. 27, 1945 COMPOSITION OF MATTER AND METHOD OF MAKING S AMEMelvin De Groote, University City, and Bernhard Keiser, -Webster Groves,Mo.. assignors to Petrolite Corporation, Ltd., Wilmington, Del., acorporation of Delaware No Drawing. Original application June 23, 1943,

Serial No. 492,185. Divided and this application April 7, 1944, SerialNo. 530,047

10 Claims.

This invention relates to a new chemical product or compound and to themanufacture and uses for the same, our present application being adivision of our parent application Serial No. 492,185, filed June 23,1943.

One object of our invention is to provide oxyalkylation derivatives ofsub-rubbery polymeric sulfur-converted polyhydric alcohol esters of thekind in which there was originally present at least twodetergent-forming monocarboxy acid radicals, each of which contains atleast one eth-' ylene linkage. These products will be described ingreater detail subsequently.

Another object is to provide a novel method of making said products.

The new chemical product herein described is an emcient demulsifier forcrude oil emulsions of the water-in-oil type, and it is also adapted foruse in other arts. For example, certain of the compositions of matterherein described are of value as surface tension depressants in theacidification of calcareous oil-bearing strata by means of a strongmineral acid, such as hydrochloric acid. Similarly. some members areeffective as surface tension depressants, or wetting agents in theflooding of exhausted oil-bearingstrata. The oxyalkylation derivativesof the kind herein described are valuable for use as break inducers indoctor treatment of sour hydrocarbons. See U. S. Patent No. 2,157,223,dated May 9, 1939, to'Sutton. Other uses are indicated subsequently.

Briefly described, our present invention consists of sub-rubberypolymeric sulfur-converted polyhydric alcohol esters of the kind inwhich there was originally present at least two detergent-forming acidradicals, each of which contains at least one ethylene linkage. Thepreferred detergent-forming acids are higher fatty acids; The preferredesters are naturally-occurring glycerides. particularly monoethylenielycerides. The preferred oxyalkylating agent is ethylene oxide. In asomewhat broader aspect, our preferred products are oxyalkylatio-nderivatives of sub-rubbery polymeric sulfur converted esters of apolyhydric alcohol, and morepartic ularly, an ester in which there ispresent at least two acyl radicals derived from unsaturated high molalmonocarboxy detergent-forming acids having at least 8, and not more than.32 carbon-atoms each.

It is known that when elemental sulfur is heated with a reactivedetergent-forming carboxylic' ularly, the formation of cyclicbisulfides.

radical. Where the oleic acid is employed in combination with apolyhydric alcohol, such as glycerol, as, for example, in triolein,which is the tri-glyceride of oleic acid, the reaction apparently doesnot stop with the formation of a simple addition product. Instead, asdiscussed in the literature, e. g., Knight 81 Stamberger, J. ChemicalSociety, London, 1928, pages 2791-8, tri-olein takes up additionalsulfur atoms, possibly even tied in through the glyceryl radical. Also,it is probable that the several fatty acid radicals present are alsolinked through sulfur atoms. Compare comparable reactions involving morereactive sulfur dichloride, and partic- Such reactions indicate therationale for thioglycerol formation, or more exactly, the formation ofsulfurized esters of thioglycerol. See Chemistry of Synthetic Resins,Ellis, 1935, volume 2, pages 1176-77. At any rate, in the course of thereaction polymers begin to be formed and a certain degree of elasticitybecomes apparent. Molecular weight determinations show the presence ofpolymers, including diads and triads (dimers, trimers) etc. Destructionof the polymeric body, for example, by saponification with alkali,results in a reduction ofthe molecular weight, loss of the elasticproperties, and apparently a return to a simpler addition product. Inour present invention we make no claim to the use of the simpleunpolymerized addition product of sulfur and an unsaturated high molalmonocarboxylic detergent-forming acid having at least 8, and not morethan 32, carbon atoms, typified by sulfurized oleic acid, as a reactant.We make no claim to the use of the free detergent-forming carboxylicacid and sulfur alone in preparing our product, but we employ the acidonly in combination with a polyhydric alcohol compound containing two ormore alcoholiform hydroxyl groups, in the form of an ester of such acidand such polyhydric alcohol.

The compound containing the two or more alcoholiform hydroxyl groups maybe a simple polyhydric alcohol, such, for example, as glycerol orethylene glycol, or it may be a condensed polyhydric alcohol likepolyglycerol, diethylene glycol, diglycerol, or triglycerol. In additionto the above polyhydric alcohols, we may also use mannitan, sorbitan,pentaerythritol, and dipentaerythritol. We may use ether alcohols, solong as they have two or more hydroxyl groups in the molecule, is.(polyhydric alcohols in which a carbon atom chain is interrupted atleast once by oxygen, as exemplified by diethylene glycol and not morethan 32, carbon atoms.

Resinous and similar materials are sometimes classified asthermoplastic, thermo-setting,

and element-convertible. The expression element-convertible refersparticularly to plastic coatings or drying oils, in which hardeningapparently is due to conversion into a new compound or composition byaction ofan element used, often oxygen. Thus, drying oils are oftenreferred to as being oxygen-convertible. For practical purposes, theonly other element finding wide application for this purpose is sulfur.Hence, certain products, and particularly certain oils, are referred toas sulfur-convertible, meaning that they react with sulfur or sulfurdichloride to yield polymeric materials, rubbery masses, or the like.

The unsaturated high molal detergent-forming monocarboxylic acidsemployed in preparing our new product or compound, are characterized byhaving a carbon atom chain, which we shall denote as R, containing atleast 8 carbon atoms, and not more than 32 carbon atoms, and which mustcontain at least one unsaturated bond, i. e., at least, one ethylenelinkage. Such acids are sometimes referred to as ethylenic.

The acyl radical may, of course, have present other non-functionalgroups, such as hydroxyl groups, acyloxy groups, etc. It is onlynecessary that the presence of such groups does not detract from (a) thedetegent-forming ability of the acids; and (b) their susceptibility tosulfur conversion. Suitability of substituted acids is indicated by verysimple tests. For instance, saponification with caustic potash, causticsoda, or the like, must yield a, soap or soap-like material. Secondly,if the detergent-form ng Prop: erties have not been eliminated by thepresence of this substituent atom or radical, then it is only necessaryto determine that susceptibility to sulfur conversion is still present.Such test is obviously the same procedure as is herein described forpreparing our new product, except that it is conducted on a small scalein the laboratcry. If the substituted acid or ester which has beenpreviously determined to have detergentf-orming properties, also showssulfur conversion susceptibility, it is, of course, the obviousfunctional equivalent of the unsubstituted or unmodified acids or estersherein described, and may be used with equal or even greatereffectiveness.

Such high molal acids may be obtained from various sources, such asoils, fats, and waxes; or one may use petroleum acids, and the like.Petroleum acids include naturally-occurring naphthenic acids and alsoacids obtained by the oxidation of hydrocarbons and waxes. Rosin acidsinclude abietic acid, pyroabietic acids, and the like. Saturated acids,such as saturated fatty acids, saturated naphthenic acids, saturatedoxidized petroleum acids, etc., can frequently'be converted into anunsaturated acid by halogenization, followed by a reaction of the kindexemplified by the internal Wurtz reaction. The 20 and 22 carbon atomacids of jojoba bean wax are suitable for conversion .into an ester, tobe usedas a reactant.

Our preference, of course, is to use unsaturated fatty acids, due totheir low cost and ready availability. One need not use a single fattyacid, but may use the mixture employed by saponification of anaturally-occurring oil or fat. For instance, special reference is madeto the fatty acids which occur naturally in olive oil, castor oil,peanut oil, cottonseed oil, fish oils, cornoil, soyabea-n .oil, linseedoil, sesame oil, lard oil, oleo oil, perilla oil, and many othernaturallyoccurring oils. Rapeseed oil, for example, contains appreciableproportions of tri-erucin, the tri-glyceride of erucic acid.

As has been previously pointed out, the high molal acids .are used inthe form of the polyhydric alcohol esterhaving at least 2 such highmolal acid radicals present. Since it is our preference to use thenaturally-occurring fatty acids, it obviously follows that ourpreference is to use the naturally-occurring glycerides. However, ifdesired, one can obtain the high molal acids from any source, andesterify such acids with various polyhydric alcohols, such as theglycols, in the conventional manner to produce suitable esters which may01' may not have a free or unreacted alcoholiform hydroxyl grouppresent. The fatty acid diglycerides typify these esterswhich contain a.free or unreacted alcoholiform hydroxyl group (in the residue of thepolyhydric alcohol, glycerol). The fatty acid tri-glycerides do notpossess this free alcoholiform hydroxyl. Both types .of glyceride, forexample, are suitable for our purpose, provided the fatty acid presentsatisfies the above expressed requirements. The manufacture of suchesters is so well known that no description is required in the presentinstance.

One may select esters of the mixed type, and such mixed esters may evencontain acyl radicals which either are not high molal in character, orare-not unsaturated, i. e., ethylenic in nature. For instance, di-oleinmay be reacted with one mole-of acetic acid, or one mole of stearic acidto give an ester which would be satisfactory for the present purpose. Asan example of amodified ester which may serve, reference is made totriacetylated triricinolein.

In those instances where an ester of a high molal detergent-forming acidof the type previously described is first reacted with a polycarboxylicacid, before any other step in the preparation of our reagent,possession of one or more alcoholiform hydroxyl groups is required toconfer reactivity. If the ester be a triglyceride, for example, thedetergent-forming acid must contain an alcoholiform hydroxyl group.Ricinoleic acid would satisfy the requirements in this case. If theester be a, diglycer-ide, the free alcoholiform vhydroxyl group presentin the glyceryl radical is sufiicient to permit the diglyceride to meetthe above requirement.

We have found that, in addition to naturallyoccurring fatty acids,addition and substitution products of fatty acids, which latter modifiedfatty acids bear a simple genetic relationship to the parent fatty acidsfrom which they were derivedare also useful for making our new chemi-'cal compound, so long as they are in part unsaturated, i. e., possesssome double bond, as shown by possession of an iodine number ofappreciable magnitude, or, in those cases where a detergent-formingcarboxylic acid is first re acted with a polycarboxylic acid inproducing our'reagent, only so "long as they possess an alcoholiformhydroxyl group also.

Instead of employing natural polyesters of reactive detergent-formingcarboxylic acids, we may use synthetic esters obtained by esterifyingone or more reactive detergent-forming carboxylic acids with apolyhydric alcohol of the kind heretofore recited and described in aconventional esterification reaction, such as reacting the alcohol withthe acid or acids in various molecularproportions in the presence of,for example, dry hydrogen chloride.

The compound produced by the interaction of a polyhydric alcohol of theabove kind and a reactive detergent-forming carboxylic acid of the abovekind will be termed a polyester" in the ,present description. In allinstances, it must contain two or more radicals or residues derived fromreactive detergent-forming carboxylic acids, which may be the same ordifferent acids; and it contains one or more radicals or residuesderived from polyhydric alcohols. Diglycerides of unsaturated fattyacids are examples of polyesters, just as are the naturally-occurringtriglycerides of unsaturated fatty acids.

The reaction of elemental sulfur with such a polyester is at first oneof simple addition of sulfur at the double bond in the'chain R of anacid residue in such polyester to form a sulfurized derivative whichdoes not differ greatly from the parent ester in properties. However,when the reaction is allowed to proceed at controlled temperatures,there is obtained a complex polymeric sulfurized product of highmolecular weight, which is semi-elastic and highly viscous, and whichapproaches the consistency of rubber, dependin upon thetime andtemperature of reaction and the proportions of reactants employed. Suchreactant must be kept in the sub-rubbery stage.

The nature of the chemical changes which take place is, to the best ofour knowledge, not yet fully understood. We have referred above to aliterature reference which suggests various mechanisms for thepolymerization process. Without attempting to express exactly thecomposition of the reagents we employ, we desire to use those polymericsulfurized bodies, obtained as above recited, which have a consistencyshort of rubber. Accordingly, we have termed them sub-rubbery to denotea range of polymerization between the simple sulfur addition products,on one hand, and the non-useable rubbers produced onsuperpolymerization, on the other.

Such sub-rubbery products are capable of dis-- We intentionally ex-.

solving in various solvents. elude sulfurized products of the kindintended as substitutes for rubber-that is, factices or similar materialof a rubbery consistency. 'This later type is insoluble in oil, butsoluble in a very limited group of solvents at the best.

The preparation of the compounds herein con-' templated consistsessentially of two separate steps, the first step being thesulfurization step of the kind previously described, and the secondbeing the oxyalkylation step. In preparing the sulfurized compound to besubjected to oxyalkylation, our preference is to proceed approximatelyasfollows: 125 parts by weight of castor oil are heated to 120 C., partsby weight of sulfur are erol and the mixture is agitated and heatedinthe presence of dry hydrogen chloride gas at a' temperature in excessof 100? C. for a period of time sufiicient to produce an ester. We havefound that reacting the mass for six hours at 150 C. is satisfactory toaccomplish this purpose. If this-procedure is tedious or undesirable,the diglyceride of ricinoleic acid may be pre pared in any other desiredmanner. For example, diglycerides are commonly prepared by treating twomoles of triglyceride with one mole of glycerol in the presence of analkaline catalyst. The ester so produced or obtained in any othersuitable manner is mixed with 15% its weight of elemental sulfur, andagitation and heat are continued until all sulfur is assimilated and aclear, transparent product is obtained, as shown by a test on glass.

As a thirdexample, the same procedure is followed as in the precedingexample, except that diolein is substituted for diricinolein.

Other esters of unsaturated fatty acids or other reactivedetergent-forming carboxylic acids of the kind heretofore mentioned maybe used instead of the castor'oil and the ricinoleic acid. For example,we have used cottonseed oil instead of castor oil in making certainexamples of our reagent, and have found it to be useful therein.However, when cottonseed oil is used, the reaction is not as smooth aswhen castor oil is employed. Also, it is usually found that longerheating is required to produce the desired reagentof optimum properties.It is, therefore, preferable to use castor oil, rather than cottonseedoil, so far aswe are now aware.

The stages of polymerisation and condensation and the elasticpropertiesv of the resulting products may be altered by varying thetemperature of the'reaction, the time of the reaction, or theproportions of reactants employed, or any combination of thesevariables. We have found that the most effective reagents are thoseobtained by reacting 100 parts by weight of the ester with from 10 to 17parts by weight of sulfur, controlling the temperature to avoid theevolution of hydrogen sulfide, so far as is practicable and employing atime sufficient to obtain highly polymerized products which are,however, still soluble. in petroleum distillates.

Having obtained a sulfurized compound or composition of the kindpreviously described, the product is subjected to oxyalkylation. Avariety of reagents containing an ethylene oxide ring may be employed.As typical examples of applicable compounds, may be mentionedepichlorhydrin,'glycide alcohol, ethylene oxide, propylene oxide,butene-Z-oxide, butene-l-oxide, isobutylene oxide, butadiene oxide,butadiene di-oxide, chloroprene oxide, isoprene oxide, decene oxide.styrene oxide, cyclohexylene oxide, cyclopentene oxide, etc. Ourpreference is to use an alkylene oxide having not more;than fourcarbonatoms, as, for example, ethylene oxide, propylene oxide,

butylene oxide, glycide, or the equivalent.

Oxyethylation of high molal compounds is well known. For instance,acids, alcohols, amides, meroaptans, and the like, are readilysusceptible to oxyethylation. The reactioninvolves a labile hydrogenatom. For example, a hydrogen atom reaction can generally be hastened bythe addi#- tion of a small amountof .an alkaline catalyst, such ascaustic soda, sodium acetate, sodium carbonate, sodium bicarbonate, orsodium methylate.

Such reactions generally take place readily, and do not requireexcessive pressure. .The steps employed in the present instance aresubstantially the same as those described in U. S. Patent No. 2,208,581,dated July 23, 1940, to Hoefielman. The time of reaction varies with theamount of alkylene oxide absorbed. This is illustrated by the followingexamples:

Example .1

Example 2 The same procedure is employed as in the preceding example,except that the amount of ethylene oxide per :mole of the ricinoleicacid is doubled; to wit, 68 lbs. used instead of 34 lbs. This was addedin two portions of 34 lbs. The time for completion of the oxyalkylationstep is somewhat longer, being 3 hours.

Example 3 The same procedure is followed as in the preceding examples,except that three times as much ethylene oxide is employed as inExample 1. This was added in three portions of 34 lbs. each. The timefor completing the oxyalkylation step is somewhat longer, to wit, 8hours.

Example 4 The same procedure is followed as in Examples 1, 2. and 3,preceding, except that sulfurized diricinolein is used instead ofsulfurized triricinolein. The preparation of the sulfurized diricinoleinhas been described previously. The molal ratios of ethylene oxide to thericinoleic radical, to wit, 3-1, 6-1 and 9-1, are preserved.

Example 5 The same procedure is followed as in Example 4, preceding,except that sulfurized d'iolein is substituted for sulfurizeddiricinolein in the preceding Example 4. Preparation of the sulfurizedolein has been described previously.

Example 6 The same procedure, is followed as in Example 4, preceding,except that sulfurized undecylenin, derived from 1 mole of glycerol and2 moles of undecylenic acid is substituted for sulfurized diricinoleinin the preceding Example 4.

Example 7 The same procedure is followed as in Example 4, preceding,except that sulfurized erucin, derived from 1 mole of g-lycero1 and 2moles of erucic acid, is substituted for sulfurized diricinolein in thePrecedingExample 4.

Emample'8 Propylene oxide, lbutyl ene oxide, o'r-"glycideis substitutedfor ethylene oxide in Examples 1 to '5, preceding. Note that the use ofpropylene oxide requires longer time for oxypropylation and may requiresomewhat higher temperature. This is true to an even greater extent ofbutylene oxide. Glycide, on the other hand, reacts much more violentlyand may react with almost explosiveviolence, even at room temperatures,or slightly elevated temperatures. Extreme precaution should be taken inhandling this latter reactant. Frequently, epichlorhydrin can besubstituted advantageously. Molal ratios of the alkylene oxide to fattyacid radical can be increased over and above the amounts exemplified inthe previous example. For instance, insteadof the present ratio of9--1., the molal ratio of 18-l or 27-1 may be employed. and a ratio in alower range such as 3-1.

In light of what has been said previously, it becomes apparent that nosatisfactory formula can be written .for a sulfurized compoundprior tooxyalkylation. It is also true that it is difii- I cult to indicate allthe points of reaction involved by oxyalkylation, and particularly, byoxyethylation. Although the compounds herein contemplated are properlydescribed as oxyalkylation derivatives of sub-rubbery .polymericsulfur-converted :polyhydric esters of the kind in which there wasoriginally present at least two detergent-forming acid radicals, each ofwhich contained at least one ethylene linkage, yet it is impossible topresent adequate chemical formula or structure. For this reason, theherein contemplated compounds must be socharacterized in the appendantclaims.

The chemical products or compounds herein described also findapplication in various industries, processes, and uses where Wettingagents of the conventional type are employed. As to some of such useswhich are well known, see The Expanding Application oi Wetting Agents,Chemical Industries, volume 48, page 324 (1941).

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is: i

1. A new chemical product or compound, comprising an oxyalkylatedderivative of a sub-rubbery polymeric sulfur-converted polyhydricalcohol ester; said ester having present, prior to sulfurization, atleast two detergent-forming monocarboxy acid radicals and each of saidacid radicals containing at least one ethylene linkage, and having atleast 8 and not more than 32 carbon atoms, the ratio of polyoxyalkyleneradicals per acid radical being within the range of 3 l to2'721.

.2. A new chemical product or compound, comprising an oxyalkylatedderivative of a sub-rubbery polymeric sulfur-converted polyhydricalcohol ester; said ester having present, prior to su1-, furization, atleast-two higher fatty acid radicals and each of aid acid radicalscontaining at least one ethylene linkage; the ratio of polyoxyalkyleneradicals per acid radical being within the range of 3:1 to 27:1.

3. A new chemical product or compound, com-:

4. A new chemical product or compound, comprising an oxyalkylatedderivative of a sub-rubbery polymeric sulfur-converted polyhydricalcohol ester; said ester having present, prior to sulfurization, atleast two higher fatty acid radicals having 18 carbon atoms and each ofsaid acid radicals containing one ethylene linkage; the ratio ofpolyoxyalkylene radicals per acid radical being within the range of 3:1to 27:1.

5. A new chemical product or compound, comprising an oxyalkylatedderivative of a sub-rubbery polymeric sulfur-converted polyhydricalcohol ester; said ester having present, prior to sulfurization, atleast two higher fatty acid radicals having 18 carbon atoms and each ofsaid acid radicals containing acid radicals containing one ethylenelinkage; the ratio of polyoxyethylene radicals per acid radical beingwithin the range of 3:1 to 27:1

6. A new chemical product or compound, comprising an oxyalkylatedderivative of a sub-rubbery polymeric sulfur-converted glyceride; saidglyceride having present, prior to sulfurization, at least twomonoethylenic higher fatty acid radical containing 18 carbon atoms; theratio of polyoxyethylene radicals per acid radical being within therange of 3:1 to 27:1. Y

7. A new chemical product or compound, combery polymericsulfur-converted erucic acid glyceride.

10. In the method of manufacturing compositions of the kind described inclaim 1, the steps of (a) sulfur-conversion of a polyhydric alcoholester to the sub-rubbery polymeric state; said ester having present,prior to sulfurization, at least two detergent-forming monocarboxy acidradicals containing at least 8 and not over 32 carbon atoms, and each ofsaid acid radicals contalning at least one ethylene linkage; and ('b)oxyalkylation of said sulfurized composition obtained by means of step(a) preceding; said oxyalkylation step soconducted that the ratio ofpolyalkylene radicals per acid radical be within the range of 3:1 to7:1.

MELVIN DE GROOTE. BERNHARD KEISER

